Bleaching using peroxyformic acid and an oxygen catalyst

ABSTRACT

A method for enhancing bleaching efficacy for treatment of articles, including for example laundry is disclosed. Methods for sanitizing and/or disinfecting and bleaching laundry and other articles is provided by washing the articles with a peroxyformic acid composition at a first pH for effective antimicrobial efficacy, thereafter applying an alkaline source to increase the pH for addition of a bleaching activator and/or catalyst for the bleaching agent at a second pH, and lastly draining the remaining components of the peroxyformic acid composition, and the bleaching agent and bleach activator/catalyst from the articles. The methods can be provided as part of a laundry cleaning operation and can be utilized in industrial and commercial applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to provisional application U.S. Ser.No. 62/523,360 filed Jun. 22, 2017, which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

Methods for enhancing bleaching efficacy for bleaching of articles,namely laundry, are provided. In particular, laundry can be treated bywashing the laundry with a peroxyformic acid composition at a first pHfor effective antimicrobial efficacy, thereafter applying an alkalinesource to increase the pH for addition of a bleaching activator and/orcatalyst for the bleaching agent at a second pH, and lastly draining theremaining components of the peroxyformic acid composition, and thebleaching agent and bleach activator/catalyst from the laundry.Beneficially, this method for bleaching laundry can be provided as partof a laundry cleaning operation and can be utilized in industrial andcommercial applications. Still further beneficially, this method forbleaching laundry can be utilized as a part of a laundry cleaningapplication that provides antimicrobial efficacy against variousdifficult to treat organisms and at various temperatures.

BACKGROUND OF THE INVENTION

In industrial and commercial laundry facilities, textile materials suchas sheets, towels, wipes, garments, table cloths, etc. are oftenlaundered at elevated temperatures at alkaline pH. Alkalinity can beprovided through a single alkaline detergent, or alternativelyalkalinity can be provided from one product, while the other detergentcomponents, including surfactants, chelants, water conditioners and/orother detergent materials are provided in a second product. In othermarkets, textile materials are often laundered with neutral detergentswith a separate alkaline product combined in a wash. Detergents can becombined in a laundry application with various additional componentssuch as bleaches, brightening agents, anti-redeposition agents, etc.that are used to enhance the appearance of the resulting textilematerials. Various additional components may optionally be dosedseparately from the alkaline detergent, and will either be mixedtogether in the laundry wash bath or in a separate laundry bath liquor.For example, in some laundry applications there are discrete dosing andrinsing steps where there is a rinse between a detergent and bleachstep. In other laundry applications, such as a tunnel washer, variousaddition steps employing mixing of the components. In each of theseapplications at the end of the cycle, the textile materials that havebeen treated with an alkaline detergent are typically treated with acommercial or industrial sour composition that contains acid componentsfor neutralizing alkaline residues on the fabric to enhance skincompatibility.

In a conventional, industrial laundry washing facility, textilematerials can be subjected to several treatment steps in an industrialsized laundry washing machine to provide antimicrobial efficacy.Exemplary treatment steps include a presoak step, a wash step that oftenoccurs at a pH of about 11 to 12, a rinse step and/or multiple rinsesteps for the removal of soil containing wash liquor which incrementallylower the pH, and a sour step that brings the final pH to about 5 to 7,and an extract step that often involves spinning the textiles to removewater. An antimicrobial composition can be applied concurrently with thedetergent, such as an all-in-one product for powders and solids orconcurrent dosing of distinct products, immediately following thedetergent step or during the sour step where it is afforded a minimumcontact time in the absence of other cleaning chemicals. Laundryapplications can vary between concurrent dosing of detergent and othercleaning chemicals.

There remains a need to improve the industrial laundry washingtechniques and provide enhanced efficacy along with other improvements,such as a reduction in processing time, cost of materials, materialconsumption, energy costs, and water consumption. Accordingly, it is anobjective of the methods to improve on one or more of these aspects oflaundry washing techniques. It is a further objective to improve theefficacy of antimicrobial and bleaching of laundry through the use ofperoxyformic acid compositions.

An object of the methods is to enhance bleaching efficacy for bleachingof laundry articles by employing a peroxyformic acid composition.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

An advantage of the methods of sanitizing and/or disinfecting andbleaching laundry is that the methods do not require high actives in ppmperoxycarboxylic acid to effectively sanitize and/or disinfect andbleach laundry when used in combination with a catalyst and/oractivator. A method for treating laundry is provided. More particularly,a method for bleaching laundry is provided.

In the instant methods, a laundry sanitizing and/or disinfecting andbleaching process is provided where the peroxyformic acid composition, adetergent composition, alkali and bleach activator and/or catalyst aredosed. This differs from certain conventional methods in various regionsby placing the sanitizing step prior to the wash step, rather thanfollowing it, providing various benefits afforded by the use of theperoxyformic acid: 1) bleach activators and/or catalysts may now be usedwith oxygen based peroxyformic acid composition for improved bleachingand antimicrobial activity; and 2) peroxyformic acid compositionsrequire lower actives in comparison to C2 or greater carbon chain fattyacid antimicrobial composition.

In an embodiment, a method of antimicrobial treatment and bleaching oflaundry includes the steps of (a) washing the laundry with aperoxyformic acid composition at a pH range from about 4 to about 7 in alaundry washing machine for antimicrobial efficacy on the laundry,wherein the peroxyformic acid composition comprises peroxyformic acid,formic acid and hydrogen peroxide; (b)adding an alkalinity source to thewashing machine to increase the pH range to at least above 9, preferablyat least about 10.5, in the laundry washing machine; (c) applying adetergent use solution to remove soil from the laundry and adding ableach activator and/or catalyst composition to boost the bleachingefficacy of the peroxyformic acid composition on the laundry in thelaundry washing machine; and (d) draining the peroxyformic acidcomposition, the detergent use solution and the bleach activator and/orcatalyst composition from the laundry. In a further embodiment of themethods, the peroxyformic acid composition has a ratio of peroxyformicacid to hydrogen peroxide of least 1:1 to about 1:1.5, or at least 1:1to about 1:2, or at least 1:1 to about 1:3, or greater and/or the methodcomprises an additional step of adding additional hydrogen peroxide tothe wash of the laundry washing machine to increase the bleachingefficacy of the peroxyformic acid composition.

In a further embodiment, the peroxyformic acid composition is applied tothe laundry in the laundry washing machine at a pH from about 5 to about7, from about 6 to about 8, or about 7. In a further embodiment, theperoxyformic acid composition is applied to the laundry in the laundrywashing machine for about 3 to about 15 minutes, or for about 5 to about10 minutes. In a further embodiment, the peroxyformic acid compositionis generated in situ or at a point of use. In a further embodiment, theperoxyformic acid composition is provided to the laundry washing machineat an actives level from about 5 ppm to about 200 ppm, or from about 5ppm to about 80 ppm.

In a further embodiment, the alkalinity source increases the pH range toat least above 10, from about 10 to about 11, or at least about 11. In afurther embodiment, the detergent use solution and the bleach activatorand/or catalyst composition is applied to the laundry in the laundrywashing machine for about 3 to about 15 minutes, or for about 5 to about10 minutes. In a further embodiment, the method includes a step ofrinsing the peroxyformic acid composition, the detergent use solutionand the bleach activator and/or catalyst composition from the laundry,including wherein the laundry is rinsed with water in the laundrywashing machine for at least about 1 minute, or from about 1 minute toabout 6 minutes. In still further embodiments, the method furthercomprises an adjuvant use solution comprising at least one of souringagents, fabric softening agents, starch, anti-wrinkle agents, sizingagents, color-fastness agents, oil and water repellant agents, waterconditioning agents, iron controlling agents, water threshold agents,soil releasing agents, soil shielding agents, optical brighteningagents, fragrances, and mixtures thereof. Still further the adjuvant usesolution is applied to the laundry in the laundry washing machine at apH from about 5 to about 8 for about 1 to about 6 minutes.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a soil removal plot depicting the bleaching efficacyaccording to methods.

FIG. 2 shows a titration for pH comparing antimicrobial activesaccording to embodiments of the methods.

FIGS. 3-5 show depictions of the methods according to embodiments ofdosing a peroxyformic acid composition for enhanced bleaching incombination with an oxygen catalyst and/or bleach activator.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particular methodsof incorporating a bleaching step in a laundering application, which canvary and are understood by skilled artisans. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

An “antiredeposition agent” refers to a compound that helps keepsuspended in water instead of redepositing onto the object beingcleaned. Antiredeposition agents are useful in the present methods toassist in reducing redepositing of the removed soil onto the surfacebeing cleaned.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, rinsing, and any combination thereof. As used herein, theterm “microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2).

The terms “include” and “including” when used in reference to a list ofmaterials refer to but are not limited to the materials so listed.

The term “laundry” refers to items or articles that are cleaned and/orreduction of microbial population in a laundry washing machine. Ingeneral, laundry refers to any item or article made from or includingtextile materials, woven fabrics, non-woven fabrics, and knittedfabrics. The textile materials can include natural or synthetic fiberssuch as silk fibers, linen fibers, cotton fibers, polyester fibers,polyamide fibers such as nylon, acrylic fibers, acetate fibers, andblends thereof including cotton and polyester blends. The fibers can betreated or untreated. Exemplary treated fibers include those treated forflame retardancy. It should be understood that the term “linen” is oftenused to describe certain types of laundry items including bed sheets,pillow cases, towels, table linen, table cloth, bar mops and uniforms.It should be understood that the term “linen” is often used to describecertain types of laundry items including bed sheets, pillow cases,towels, table linen, table cloth, bar mops and uniforms.

As used herein, the term “peracid” may also be referred to as a“peroxycarboxylic acid”, “percarboxylic acid” or “peroxyacid.”Sulfoperoxycarboxylic acids, sulfonated peracids and sulfonatedperoxycarboxylic acids are also included within the term “peracid” asused herein. The terms “sulfoperoxycarboxylic acid,” “sulfonatedperacid,” or “sulfonated peroxycarboxylic acid” refers to theperoxycarboxylic acid form of a sulfonated carboxylic acid as disclosedin U.S. Patent Publication Nos. 2010/0021557, 2010/0048730 and2012/0052134 which are incorporated herein by reference in theirentireties. A peracid refers to an acid having the hydrogen of thehydroxyl group in carboxylic acid replaced by a hydroxy group. Oxidizingperacids may also be referred to herein as peroxycarboxylic acids.

As used herein, the term “polymer” generally includes, but is notlimited to, homopolymers, copolymers, such as for example, block, graft,random and alternating copolymers, terpolymers, and higher “x”mers,further including their derivatives, combinations, and blends thereof.Furthermore, unless otherwise specifically limited, the term “polymer”shall include all possible isomeric configurations of the molecule,including, but are not limited to isotactic, syndiotactic and randomsymmetries, and combinations thereof. Furthermore, unless otherwisespecifically limited, the term “polymer” shall include all possiblegeometrical configurations of the molecule.

The term “soft surface” refers to a resilient cleanable substrate, forexample materials made from woven, nonwoven or knit textiles, leather,rubber or flexible plastics including fabrics (for example surgicalgarments, draperies, bed linens, bandages, etc.), carpet, transportationvehicle seating and interior components and the like. As referred toherein laundry and linens are included in soft surfaces.

As used herein, the term “soil” refers to polar or non-polar organic orinorganic substances including, but not limited to carbohydrates,proteins, fats, oils and the like. These substances may be present intheir organic state or complexed to a metal to form an inorganiccomplex.

As used herein, the term “stain” refers to a polar or non-polarsubstance which may or may not contain particulate matter such as metaloxides, metal hydroxides, metal oxide-hydroxides, clays, sand, dust,natural matter, carbon black, graphite and the like

As used in this disclosure, the term “sporicide” refers to a physical orchemical agent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores ofBacillus cereus or Bacillus subtilis within a defined time frame andtemperature set by the relevant regulatory authority. In certainembodiments, the sporicidal compositions of the invention providegreater than a 99% reduction (2-log order reduction), greater than a99.99% reduction (4-log order reduction), or greater than a 99.999%reduction (5-log order reduction) in such population.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Theefficacy according to the methods is effective against a broad range ofbacteria, including gram positive and gram negative. Exemplary bacteriainclude for example, Escherichia spp., Staphylococcus spp., Klebsiellaspp., Enterococcus spp., Acinetobacter spp., Pseudomonas spp.,Streptococcus spp., including for example Escherichia Coli,Staphylococcus aureus, methicillin-resistant Staphylococcus aureus(MRSA), Staphylococcus epidermidis, Klebsiella Pneumonia includingCarbapenem Resistant Klebsielle Pneumonia, Enterococcus faecalis,Enterococcus hirae, Acinetobacter baumannii, Pseudomonas aeruginosa,Streptococcus pyogenes, Mycobacterium terrae, and Mycobacterium avium.In addition to bacteria it is understood that viruses, fungi,Mycobacteria, yeast and spores can also be treated by the methodsdisclosed herein.

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

The term “threshold agent” refers to a compound that inhibitscrystallization of water hardness ions from solution, but that need notform a specific complex with the water hardness ion. Threshold agentsinclude but are not limited to a polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

The term “water soluble” refers to a compound that can be dissolved inwater at a concentration of more than 1 wt. %. The terms “sparinglysoluble” or “sparingly water soluble” refer to a compound that can bedissolved in water only to a concentration of 0.1 to 1.0 wt. %. The term“water insoluble” refers to a compound that can be dissolved in wateronly to a concentration of less than 0.1 wt. %.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods, systems, and compositions of the present invention maycomprise, consist essentially of, or consist of the components andingredients of the present invention as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods, systems, and compositions may include additional steps,components or ingredients, but only if the additional steps, componentsor ingredients do not materially alter the basic and novelcharacteristics of the claimed methods, systems, and compositions.

It should also be noted that, as used in this specification and theappended claims, the term “configured” describes a system, apparatus, orother structure that is constructed or configured to perform aparticular task or adopt a particular configuration. The term“configured” can be used interchangeably with other similar phrases suchas arranged and configured, constructed and arranged, adapted andconfigured, adapted, constructed, manufactured and arranged, and thelike.

Methods of Antimicrobial Treatment (Sanitizing and/or Disinfecting) andBleaching Laundry

Washing Machines

A method for treating laundry is provided. A laundry washing machine isprovided. The laundry washing machine includes a drum having an interiorfor holding laundry, a motor constructed and arranged for rotating thedrum, a water inlet for introducing water into the drum interior, achemical inlet for introducing chemicals into the drum interior, a drainfor allowing fluid to drain from the drum interior, and a processingunit constructed for operating the laundry washing machine. Theprocessing unit can be constructed to provide a washing cycle forwashing laundry, an antimicrobial , disinfecting and bleaching cycle(which may be before or after the washing cycle), and a detergent usesolution with a bleach activator and/or catalyst cycle for removing soilfrom the laundry and boosting the bleaching of the peroxyformic acidaccording to the methods.

The method for treating laundry can be provided in a commercial and/orindustrial laundry washing facility and can be provided in a residentialand/or home laundry washing machine that is programmable. Exemplarycommercial and/or industrial laundry washing facilities include thosecleaning textiles for the rental, health care, and hospitalityindustries. In addition, the method for treating laundry can occur aspart of an operation that includes additional steps, such as, washing,rinsing, finishing, and extracting. In addition, it should be understoodthat the step of treating laundry can include, as part of the step,additional activities such as, for example, washing and finishing.

Many commercial and industrial laundry washing machines are capable ofhandling the method for treating laundry according to the methods. Manycommercial and industrial laundry washing machines are computerprogrammable, and computer programs can be provided to operate themachines according to the methods. In addition, it is expected thatmachines can be made available to treat laundry according to themethods, and that these machines can be used in both industrial andcommercial applications and in home and residential applications. Inaddition, the treatment composition can be formulated so that it can beused in commercial and industrial laundry washing machines andresidential laundry washing machines that are in common use, and arecomputer programmable, without modification.

In some embodiments, the methods are suitable for use inwasher-extractor machines. In an embodiment, the methods can be appliedin a front loading horizontal axis washer. In another embodiment, themethods can be applied in a top loading washer. Laundry washing machinesthat can be used according to the methods can be characterized ashorizontal axis or vertical axis washers depending upon the axis ofrotation.

In other embodiments, tunnel washers and continuous bath washers can beutilized according to the methods. A tunnel washer consists of severalcompartments that are arranged in a tunnel-like construction. Thelaundry remains in each compartment for a certain time and then istransported to the next compartment by top-transfer or bottom-transfer.Each compartment can be connected to a dosing unit that allows theaddition of one or more laundry components. In this way, the cleaningand disinfecting composition of the first component and the bleachingand disinfecting composition of the second component, as well as otherchemicals for the treatment of the laundry cam be added independentlyinto various compartments of the tunnel washer.

Laundry/Textiles

Any of a variety of textile articles can benefit from being washedaccording to the present method. Suitable textile articles include thosefrom hospitality, health care, industrial, and food service facilities.In an embodiment, the textile cleaned by the present is a white textilearticle or a colored synthetic (e.g., polyester) textile article. In anembodiment, the textile is a white cotton textile article. In anembodiment the textile articles are from a health care facility. Thatis, the textiles are textile articles employed in health care. Suchhealth care textile articles include, for example, a sheet, a towel, apatient gown, a bed spread, an incontinence pad, an operating roomlinen, a scrub, a wash cloth, a pillow case, or a mixture thereof.

Methods

A general depiction of the methods is shown in FIGS. 3-4. In anembodiment the methods include at least providing a peroxyformic acidcomposition for disinfection and/or bleaching; thereafter increasing thepH of the wash with an alkalinity source to increase pH into the rangewhere the oxygen catalyst is effective; providing a catalyst to activateavailable oxygen in the peroxyformic acid composition to improvebleaching at low temperatures; and optionally adding additionalbleaching composition. As used herein, the phrase “low temperature”refers to a temperature of about 50° C. at the most.

The laundry treatment methods can provide for antimicrobial andbleaching treatment and employ a peroxyformic acid composition. Theperoxyformic acid composition comprises peroxyformic acid, formic acidand hydrogen peroxide. Additional components can be included in theperoxyformic acid composition. The peroxyformic acid composition can beprovided in the form of a concentrate that is diluted with water toprovide a use solution. The use solution can be used for washingarticles such as laundry.

The method for treating laundry can be provided as part of an overallmethod for cleaning laundry. That is, as part of a laundry cleaningoperation, the laundry can be treated with an antimicrobial andbleaching composition to provide antimicrobial and bleaching properties.The antimicrobial properties can be characterized as sanitizing whenthere is a substantial reduction of bacteria, fungi, spores, and othermicroorganisms or microorganism generating materials on a surface beingtreated to provide a sanitized surface. A substantial reduction refersto a reduction of at least three orders of magnitude and can be referredto as a three-logio reduction. Preferably, the reduction can be at leastfour orders of magnitude, and more preferably at least five orders ofmagnitude.

The method for treating laundry refers to the treatment of laundry withthe peroxyformic acid composition as substantially shown and depicted inFIGS. 3-5. The methods include the step of washing the laundry with aperoxyformic acid composition at a pH range from about 4 to about 7 forantimicrobial efficacy, followed by adding an alkalinity source to thewashing machine to increase the pH to an alkaline range for thedetergent composition containing a bleach activator (FIG. 3), catalyst(FIG. 4) or combination (FIG. 5) for bleaching efficacy, and thereafterdraining the PFA, bleach catalyst and/or activator. As referred toherein, the detergent composition can include surfactants, cleaningagents and other components conventionally formulated into detergents;however in an additional embodiment, the detergent composition canconsist or consist essentially of the bleach activator and/or bleachcatalyst. In some embodiments where the detergent composition is neutralor low alkaline detergent an additional step of adding alkalinity beforeor simultaneous to dosing the detergent composition can be included inthe methods. In a still further embodiment, the PFA and detergent and/oralkalinity source could be dosed simultaneously, such variousembodiments are included within the scope of the methods described anddepicted herein.

In some embodiments the washing step employing a peroxyformic acidcomposition may be preceded by an initial washing step (shown asoptional in FIGS. 3-5). In some embodiments the initial washing step isnot a highly alkaline step; it could include a neutral step or lowalkaline step and in such embodiments the peroxyformic acid is able todecrease the pH on its own. However in some embodiments, an initialwashing step that is more alkaline is not preferred as the method wouldrequire the step of decreasing the pH to the desired range (such asbetween about 4 and about 8) for the antimicrobial efficacy of theperoxyformic acid following an initial washing step (such as an alkalinedetergent composition).

The methods can further include the step of adding additional hydrogenperoxide (or active oxygen) to the wash (FIG. 5) to further enhance thebleaching efficacy of the methods. The addition of the additionalhydrogen peroxide (or active oxygen) can be added to the system atvarious points, as shown in FIG. 5, including for example,before/simultaneous/after the peroxyformic acid composition,before/simultaneous/after the alkalinity source, and/orbefore/simultaneous/after the detergent composition.

The conditions for employing the peroxyformic acid composition includecontacting the laundry with the peroxyformic acid composition at a pHfrom about 2 to about 10, from about 2 to about 9, from about 2 to about8, from about 4 to about 9, from about 4 to about 8, from about 4 toabout 7, from about 5 to about 8, or preferably less than about 7 toprovide a pH that favors the antimicrobial treatment. In someembodiments a pH of at least 4 is preferred to ensure an acidic pH doesnot damage the fabric of the laundry and less than about 7 for microefficacy of the peroxyformic acid. In preferred embodiments, thetreatment of laundry with the peroxyformic acid composition is at a pHfrom about 4 to about 7, or more preferably form about 5 to about 7, andmost preferably form about 6 to about 7. In an aspect, the method ofapplying the peroxyformic acid composition to the laundry in the laundrywashing machine is for a period of time of at least a few minutes, orabout 3 to about 15 minutes, or for about 5 to about 10 minutes. Ingeneral, it is expected that sufficient antimicrobial effect can occurat a time of between about 1 and about 20 minutes, at a time of betweenabout 2 and about 15 minutes, and a time of between about 3 minutes andabout 10 minutes.

Thereafter, the method for treating laundry includes the step of addingan alkalinity source to the washing machine to increase the pH range toat least about 7, at least above 8, above 9, above 10, from about 10 toabout 11, or at least about 11. Any suitable alkalinity source can beemployed according to the methods. Exemplary alkalinity sources includeat least one of alkali metal hydroxide, alkali metal silicate, alkalimetal carbonate or other base components. As a skilled artisan willappreciate, the increase in pH by the alkalinity source is pH dependent.A lower temperature range employed in the antimicrobial and/or bleachingstep will require a lower pH adjustment.

Thereafter, the method for treating laundry includes the providing of adetergent use solution and a bleach activator and/or catalyst at analkaline pH, at a pH greater than about 7, preferably at a pH from about9 to about 13 to provide a pH that favors bleaching efficacy. Thedetergent use solution and the bleach activator and/or catalystcomposition is applied to the laundry in the laundry washing machine forabout 3 to about 15 minutes, or for about 5 to about 10 minutes. Ingeneral, it is expected that sufficient bleaching can occur at a time ofbetween about 1 and about 20 minutes, at a time of between about 2 andabout 15 minutes, and a time of between about 3 minutes and about 10minutes.

The detergent use solution can be a neutral to highly alkaline detergentuse solution. In general, it is expected that an alkaline wash refers toa wash that takes place at a pH at between about 7 and about 13, and caninclude a pH of between about 8 and about 12. As referred to hereindetergent use solutions include an alkalinity agent. Exemplaryalkalinity agents include at least one of alkali metal hydroxide, alkalimetal silicate, alkali metal carbonate or other base components. Thedetergent use solution can further include any one or more ofsurfactants, chelants, polymers, enzymes, or other functionalingredients.

The method for treating laundry can optionally include the additionalstep of adding hydrogen peroxide to the wash of the laundry washingmachine to increase the bleaching efficacy of the peroxyformic acidcomposition. The additional hydrogen peroxide added to the washingmachine to increase the bleaching efficacy can be dosed at variouspoints in the method, including before/simultaneous/after theperoxyformic acid composition, before/simultaneous/after the alkalinitysource, and/or before/simultaneous/after the detergent composition.

The method for treating laundry can optionally include the additionalstep of rinsing the peroxyformic acid composition, the detergent usesolution and the bleach activator and/or catalyst composition from thelaundry. In an aspect, the laundry is rinsed with water in the laundrywashing machine for at least about 1 minute, or from about 1 minute toabout 6 minutes. Beneficially, according to the methods the peroxyformicacid composition degrades into its inert components and therefore doesnot remain in the laundry solution as long as conventional biocidesand/or other sanitizing components. Therefore, the rinsing and drainingstep in effect removes the detergent use solution and the bleachactivator and/or catalyst composition from the laundry. As depicted inthe figures the various draining steps can optionally include a rinsingstep before or after the draining. The method for treating laundry canoptionally include the additional step of adding an adjuvant usesolution comprising at least one of souring agents, fabric softeningagents, starch, anti-wrinkle agents, sizing agents, color-fastnessagents, oil and water repellant agents, water conditioning agents, ironcontrolling agents, water threshold agents, soil releasing agents, soilshielding agents, optical brightening agents, fragrances, and mixturesthereof. In an aspect, the addition of the adjuvant use solution can beadded at any step of the process to enhancing the cleaning and/or thesanitizing and/or disinfecting and bleaching of the laundry. In anaspect, the adjuvant use solution is applied to the laundry in thelaundry washing machine at a pH from about 5 to about 8 for about 1 toabout 6 minutes.

Although not depicted in the figures, in a preferred embodiment, afinishing or sour step is added after the draining of the peroxyformicacid and bleach compositions. In such embodiments, any number ofdraining and/or rinsing steps can be precede the finishing or sour step.

In an preferred aspect, the method of sanitizing and/or disinfecting andbleaching laundry precedes a further washing step to disinfect thelaundry and remove bacteria, viruses or other contaminants from thelaundry. Beneficially, according to such an aspect, the disinfectingkills the bacteria, viruses or other contaminants before any wash watersare discharged from the laundry washing machine. However, in otheraspects, the method of sanitizing and/or disinfecting and bleachinglaundry follows an initial washing step for the laundry.

Peroxyformic Acid Compositions

The peroxyformic acid compositions provide the antimicrobial andbleaching efficacy according to the methods. It is desirable to providethe treatment use composition at a pH that favors antimicrobial andbleaching treatment first at a relatively low pH to effect a desiredlevel of antimicrobial treatment and the bleaching at a higher pH (asachieved by dosing the alkalinity source) in order to effect the desiredlevel of bleaching through use of a bleach activator and/or catalystwhich is effective for bleaching without damaging the laundry (e.g.textile substrates) at alkaline pH. As one skilled in the artunderstands the use of bleaching component at a more acidic pH can causedamage to the laundry. Moreover, in order to take advantage of thepossible carryover effect from a washing step that uses an alkalinedetergent use solution, it can be advantageous to first provide theperoxyformic acid composition at the relatively low pH, then perform awashing step with an alkaline detergent that provides the bleachingoperation with a pH that favors bleaching.

The peroxyformic acid compositions can include equilibrium ornon-equilibrium compositions comprising, consisting of and/or consistingessentially of peroxyformic acid, formic acid, hydrogen peroxide andwater. Additional components can be included in the peroxyformic acidcomposition. A peroxyformic acid composition can be provided to a washmachine as a concentrate or a use solution. A peroxyformic acidcomposition can be generated onsite or off-site and provided to a washmachine.

In some embodiments, the peroxyformic acid compositions according to themethods include a higher ratio of hydrogen peroxide, such as found inconventional peracid compositions. In an aspect, the ratio ofperoxyformic acid to hydrogen peroxide is about 1:1 to about 1:2, about1:1 to about 1:1.5. In an additional aspect, the ratio of peroxyformicacid to hydrogen peroxide can be lower, including embodiments having alower ratio of hydrogen peroxide in comparison to other peroxycarboxylicacids, and additional hydrogen peroxide can be added to the methods. Insuch an aspect, the ratio of peroxyformic acid to hydrogen peroxide canbe at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1,at least 9:1, at least 10:1, at least 11:1, at least 12:1, at least13:1, at least 14:1, at least 15:1, at least 16:1, at least 17:1, atleast 18:1, at least 19:1, at least 20:1, at least 21:1, at least 22:1,at least 23:1, at least 24:1, at least 25:1, at least 26:1, at least27:1, at least 28:1, at least 29:1, or at least 30:1, and combined withadditional hydrogen peroxide added to the methods.

In an aspect, the peroxyformic acid composition is provided at anactives level from about 5 ppm to about 200 ppm, from about 5 ppm toabout 100 ppm, from about 5 ppm to about 80 ppm, from about 10 ppm toabout 80 ppm, or preferably from about 20 ppm to about 80 ppm. In morepreferred embodiments, the peroxyformic acid composition is provided atan actives level from about 5 ppm to about 80 ppm, or about 5 ppm toabout 40 ppm. In a beneficial aspect of the methods described herein,the peroxyformic acid composition can be dosed at a lower active levelin comparison to other peroxycarboxylic acid compositions, such asperoxyacetic acid. This is a benefit to the methods as the greaterantimicrobial activity of the peroxyformic acid composition permits theuse of a lower amount of the peroxycarboxylic acid and thereforeovercomes the lower pKa of the acid which is generally a disadvantage ofa laundering method requiring a step of neutralizing the acid with analkalinity source. Peroxyformic acid compositions can be generatedthrough reaction of an ester of a polyhydric alcohol and formic acid andhydrogen peroxide or a substance that generates hydrogen peroxide whenin contact with a liquid, as disclosed in U.S. Pat. No. 9,518,013, whichis incorporated by reference. Peroxyformic acid compositions can also begenerated through a reaction of formic acid and hydrogen peroxide or asubstance that generates hydrogen peroxide when in contact with aliquid, as disclosed in U.S. Patent Publication No. 2016/0176814, whichis incorporated by reference. Various reactions for generatingperoxyformic acid (alone or in combination with additional peracids) canbe achieved through use of on-site generators, including those disclosedin U.S. Pat. Nos. 8,858,895 and 9,192,909, and U.S. Patent PublicationNo. 2017/0064949, which is incorporated by reference.

Peroxyformic Acid Generated with Formic Acid

Peroxyformic acid compositions can be generated through reaction offormic acid and hydrogen peroxide or a substance that generates hydrogenperoxide when in contact with a liquid. A method for formingperoxyformic acid comprises contacting formic acid with hydrogenperoxide to form a resulting aqueous composition that comprises aperacid that comprises peroxyformic acid, wherein before saidcontacting, the ratio between the concentration of said formic acid(w/v) and the concentration of said hydrogen peroxide (w/v) is about 2or higher, and the ratio between the concentration of said peracid (w/w)and the concentration of hydrogen peroxide (w/w) in said formedresulting aqueous composition reaches about 2 or higher at least within4 hours, or preferably 2 hours of said contacting. The formic acid canbe provided in any suitable way. In some embodiments, before thecontacting step, the formic acid can be provided in a composition thatcomprises formic acid, e.g., an aqueous solution that comprises formicacid. In other embodiments, before the contacting step, the formic acidcan be provided in a composition that comprises a substance thatgenerates formic acid upon contact with an aqueous composition. Anysuitable substance that generates formic acid can be used in the presentmethods. The substance can be a salt of formate, e.g., a sodium orammonium salt of formate, or an ester of formate. Exemplary esters offormate include glycerol formates, pentaerythritol formates, mannitolformates, propylene glycol formates, sorbitol formates and sugarformates. Exemplary sugar formates include sucrose formates, dextrinformates, maltodextrin formates, and starch formates. In someembodiments the formates may be provided in a solid composition, such asa starch formate.

The hydrogen peroxide used in the present methods can be provided in anysuitable way. In some embodiments, before the contacting step, thehydrogen peroxide can be provided in a composition that compriseshydrogen peroxide, e.g., an aqueous solution that comprises hydrogenperoxide. In other embodiments, before the contacting step, the hydrogenperoxide can be provided in a composition that comprises a substancethat generates hydrogen peroxide upon contact with an aqueouscomposition. Any suitable substance that generates hydrogen peroxide canbe sued in the present methods. The substance can comprise a precursorof hydrogen peroxide. Any suitable precursor of hydrogen peroxide can beused in the present methods. For example, the precursor of hydrogenperoxide can be sodium percarbonate, sodium perborate, urea hydrogenperoxide, or PVP-hydrogen peroxide.

In some embodiments, formic acid provided in a first aqueous compositionis contacted with hydrogen peroxide provided in a second aqueouscomposition to form peroxyformic acid in the resulting aqueouscomposition. In other embodiments, formic acid provided in a firstaqueous composition is contacted with a substance that generateshydrogen peroxide upon contact with an aqueous composition provided in asecond solid composition to form peroxyformic acid in the resultingaqueous composition. In still other embodiments, a substance thatgenerates formic acid upon contact with an aqueous composition providedin a first solid composition is contacted with hydrogen peroxideprovided in a second aqueous composition to form peroxyformic acid inthe resulting aqueous composition. In yet other embodiments, a substancethat generates formic acid upon contact with an aqueous compositionprovided in a first solid composition and a substance that generateshydrogen peroxide upon contact with an aqueous composition provided in asecond solid composition are contacted with a third aqueous compositionto form peroxyformic acid in the resulting aqueous composition. In yetother embodiments, a substance that generates formic acid upon contactwith an aqueous composition and a substance that generates hydrogenperoxide upon contact with an aqueous composition are provided in afirst solid composition, and the first solid composition is contactedwith a second aqueous composition to form peroxyformic acid in theresulting aqueous composition. The resulting aqueous composition thatcomprises a peracid that comprises peroxyformic acid can be any suitabletypes of aqueous compositions. For example, the resulting aqueouscomposition can be an aqueous solution. In another example, theresulting aqueous composition can be an aqueous suspension.

Before the contacting step, the ratio between the concentration of theformic acid (w/v) and the concentration of the hydrogen peroxide (w/v)can be in any suitable range. In some embodiments, before thecontacting, the ratio between the concentration of the formic acid (w/v)and the concentration of the hydrogen peroxide (w/v) can be from about 2to about 100, e.g., about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10,10-15, 15-20, 20-25, 25-30, 30-35, 35-40, 40-45 or 45-50 or greater fromabout 50-100. The ratio between the concentration of the peracid (w/w)and the concentration of hydrogen peroxide (w/w) in the formed aqueouscomposition can reach any suitable range. In some embodiments, the ratiobetween the concentration of the peracid (w/w) and the concentration ofhydrogen peroxide (w/w) in the formed aqueous composition can reach,within about 4 hours, or preferably 2 hours of the contacting, fromabout 2 to about 1,500, e.g., about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9,9-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35-40, 40-45, 45-50, 50-60,60-70, 70-80, 80-90, 90-100, 100-200, 200-300, 300-400, 400-500,500-600, 600-700, 700-800, 800-900, 900-1,000, 1,000-1,100, 1,100-1,200,1,200-1,300, 1,300-1,400, or 1,400-1,500. In other embodiments, theratio between the concentration of the peracid (w/w) and theconcentration of hydrogen peroxide (w/w) in the formed aqueouscomposition reaches at least about 10 within about 30 minutes of thecontacting, preferably at least about 10-40 within about 30 minutes ofthe contacting.

The formed aqueous composition can comprise any suitable concentrationof hydrogen peroxide. In some embodiments, the formed aqueouscomposition can comprise about 5% (w/w) or less hydrogen peroxide, e.g.,about 5% (w/w), 4.5% (w/w), 4% (w/w), 3.5% (w/w), 3% (w/w), 2.5% (w/w),2% (w/w), 1.5% (w/w), 1% (w/w), 0.9% (w/w), 0.8% (w/w), 0.7% (w/w), 0.6%(w/w), 0.5% (w/w), 0.4% (w/w), 0.3% (w/w), 0.2% (w/w), 0.1% (w/w), 0.05%(w/w), 0.01% (w/w), 0.005% (w/w), or 0.001% (w/w) of hydrogen peroxide.In other embodiments, the formed aqueous composition reaches about 2%(w/w) or less hydrogen peroxide within at least about 4 hours, orpreferably 2 hours of the contacting. In still other embodiments, theformed aqueous composition reaches about 1% (w/w) or less hydrogenperoxide within at least about 1 hour of the contacting. In yet otherembodiments, the formed aqueous composition reaches about 0% (w/w) toabout 0.001% (w/w) hydrogen peroxide and maintains about 0% (w/w) toabout 0.001% (w/w) hydrogen peroxide for at least 1 hour.

The present methods can be conducted in the presence of a catalyst. Anysuitable catalyst can be used in the present methods. In someembodiments, the catalyst can be a mineral acid, e.g., sulfuric acid,methanesulfonic acid, nitric acid, phosphoric acid, pyrophosphoric acid,polyphosphoric acid or phosphonic acid. The present methods can also beconducted in the presence of a cation acid exchange resin system. Anysuitable cation acid exchange resin system can be used in the presentmethods. In some embodiments, the cation acid exchange resin system is astrong cation acid exchange resin system. In other embodiments, the acidexchange resin system is sulfonic acid exchange resin, e.g.,commercially-available as Dowex M-31 or Nafion.

The resulting aqueous composition can comprise a stabilizing agent forthe peracid. Any suitable stabilizing agents can be used in the presentmethods. Exemplary stabilizing agents include a phosphonate salt(s)and/or a heterocyclic dicarboxylic acid, e.g., dipicolinic acid.

The present methods can further comprise a step of reducing theconcentration of the hydrogen peroxide in the resulting aqueouscomposition. The concentration of the hydrogen peroxide in the resultingaqueous composition can be reduced using any suitable methods. Forexample, the concentration of the hydrogen peroxide in the resultingaqueous composition can be reduced using a catalase or a peroxidase.

Peroxyformic Acid Generated with Esters of a Polyhdric Alcohol andFormic Acid

Peroxyformic acid compositions can be generated through reaction of anester of a polyhydric alcohol and formic acid and hydrogen peroxide or asubstance that generates hydrogen peroxide when in contact with aliquid. Peroxyformic acid forming compositions according to the methodscomprise: a) a first reagent that comprises an ester of a polyhydricalcohol and formic acid, and b) a second reagent that comprises hydrogenperoxide or that comprises a substance that generates hydrogen peroxidewhen in contact with a liquid, wherein 1) said first reagent and saidsecond reagent are kept separately prior to use, and when it is time togenerate peroxyformic acid, said first reagent and said second reagentare configured to be contacted with each other to form a liquid thatcomprises peroxyformic acid and has a pH below about 11, and pH of theformed liquid becomes about 8 or lower within about 1 minute after thecontact between said first reagent and said second reagent; or 2) saidsecond reagent comprises a substance that generates hydrogen peroxidewhen in contact with a liquid, said first reagent and said secondreagent are comprised in a solid composition, and when it is time togenerate peroxyformic acid, said solid composition is configured to becontacted with a liquid to form a liquid that comprises peroxyformicacid and has a pH below about 11, and pH of the formed liquid becomesabout 8 or lower within about 1 minute after the contact between saidsolid composition and said liquid.

The present peroxyformic acid forming compositions can comprise anysuitable ester of a polyhydric alcohol and formic acid. Typically, apolyhydric alcohol refers to a molecule with two or more hydroxyl (—OH)groups. An ester of a polyhydric alcohol and formic acid refers to anester formed between a polyhydric alcohol and formic acid. Esters asreferred to herein are considered ‘water-less’ systems as no additionalwater is added to the reaction. In some embodiments, the presentperoxyformic acid forming compositions comprise glycerol formates,pentaerythritol formates, mannitol formates, propylene glycol formates,sorbitol formates and sugar formates. The present peroxyformic acidforming compositions can comprise any suitable sugar formates, e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates.

In a preferred embodiment, a liquid reaction employs glycerol formates,pentaerythritol formates, mannitol formates, or propylene glycolformates. In a still further preferred embodiment, a liquid reactionemploys glycerol formates. Beneficially, the glycerol formates rapidlyundergo hydrolysis for peroxyformic acid generation according to themethods. In an aspect, the precursors provided do not include additionalwater added into the system which would negatively interfere with thekinetics of the reaction between the ester of a polyhydric alcohol andformic acid and hydrogen peroxide. In an aspect, the premixes and theperoxyformic acid forming composition do not add free water into thesystems, which would negatively interfere with the ester, e.g. glycerolformates.

In a preferred embodiment, a solid reaction employs sugar formates e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates. In a still further preferred embodiment, a solid reactionemploys starch formates.

The present peroxyformic acid forming compositions can comprise a usesolution or a concentrate of the ester of a polyhydric alcohol andformic acid. In some aspects, the methods generate a peroxyformic acidthrough a concentrate reaction of the ester of a polyhydric alcohol andformic acid. In other aspects, the methods generate a peroxyformic acidthrough a diluted use solution reaction of the ester of a polyhydricalcohol and formic acid.

The first or second reagent can have any suitable pH range in thepresent peroxyformic acid forming compositions. For example, the firstor second reagent can have a pH below about 11, or from about −2 toabout 11, or from about 0 to about 11, e.g., about −2 to about −1, −2 toabout 0, 0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2,1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7,2-8, 2-9, 2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5,4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7,6-8, 6-9, 6-10, 6-11, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10,9-11, 10-11, or at about −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.In some embodiments, the first or second reagent has a pH ranging fromabout 5 to about 10, e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8,6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, or 9-10. In other embodiments, thefirst or second reagent has a pH at about 9.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid and has any suitable pH, including a pHbelow about 11, or from about −2 to about 11, or from about 0 to about11, e.g., about −2 to about −1, −2 to about 0, 0-1, 0-2, 0-3, 0-4, 0-5,0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9,1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5,3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11,5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11, 6-7, 7-8,7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or at about −2, −1,0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the firstreagent and the second reagent are configured to be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid and has a pH ranging from about −2 to about 11, 0 to about 10, or 5to about 10, e.g., about −2-0, 0-1, 1-2, 2-3, 3-4, 4-5, 5-6, 5-7, 5-8,5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, 9-10, or10-11. In other embodiments, the first reagent and the second reagentare configured to be contacted with each other to form a liquid, e.g., asolution, that comprises peroxyformic acid and has a pH at about 9. In apreferred aspect, the formed liquid, e.g., a solution, that comprisesperoxyformic acid and has a pH near neutral, from about 6-7.

The pH of the formed liquid can become about 8 or lower within about 1minute after the contact between the first reagent and the secondreagent or after the contact between the solid composition and theliquid. In some embodiments, the pH of the formed liquid can becomeabout 8 or lower within about 1 second, 2 seconds, 3 seconds, 4 seconds,5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds after the contact betweenthe first reagent and the second reagent or after the contact betweenthe solid composition and the liquid. In other embodiments, the pH ofthe formed liquid comprising peroxyformic acid becomes about 8 or lowerwithin about 1 minute or less. In an aspect, the pH of the formed liquidcomprising peroxyformic acid becomes about 8 or lower within about 45seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds orless, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10seconds or less, or 5 seconds or less. In an aspect, the pH of theformed liquid comprising peroxyformic acid becomes about 8 or lower nearinstantaneously. In other embodiments, the pH of the formed liquid canbecome about lower than −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, or 8 withinabout 1 minute after the contact between the first reagent and thesecond reagent or after the contact between the solid composition andthe liquid.

The liquid that comprises peroxyformic acid can maintain the pH rangingfrom about −2 to about 8, or from about 0 to about 8 for any suitabletime after the contact between the first reagent and the second reagent,or after the contact between the composition and a liquid. In someembodiments, the liquid that comprises peroxyformic acid maintains thepH ranging from about −2 to about 8, or from about 0 to about 8 fromabout 1 second to about 10 hours after the contact between the firstreagent and the second reagent or after the contact between thecomposition and a liquid. For example, the liquid that comprisesperoxyformic acid can maintain the pH at about −2, −1, 0, 1, 2, 3, 4, 5,6, 7, or 8 from about 1 second to about 10 hours after the contactbetween the first reagent and the second reagent or after the contactbetween the composition and a liquid. In another example, the liquidthat comprises peroxyformic acid can maintain the pH ranging from about0 to about 8 for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9hours, or 10 hours. In a preferred aspect, the formed liquid, e.g., asolution, that comprises peroxyformic acid and has a pH near neutral,from about 6-7 in a use solution.

In some embodiments, the first reagent and the second reagent areconfigured to be contacted with each other to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 4 to about 8or 9, e.g., about 4-5, 5-6, 6-7, 7-8, or 8-9. In a preferred aspect, theformed liquid, e.g., a solution, that comprises peroxyformic acid andhas a pH near neutral, from about 6-7 in a use solution. In one example,the first reagent and the second reagent are configured to be contactedwith each other to form a solution that comprises peroxyformic acid andhas a pH ranging from about 6 to about 8 or 9. The first reagent and thesecond reagent can be configured to be contacted with each other to forma solution that comprises peroxyformic acid and has a pH ranging fromabout 4 to about 8 or 9, and the solution can maintain the pH range forany suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours.

In other embodiments, the solid composition is configured to becontacted with a liquid to form a solution that comprises peroxyformicacid and has a pH ranging from about 4 to about 8 or 9, e.g., about 4-5,5-6, 6-7, 7-8, or 8-9. In one example, the solid composition isconfigured to be contacted with a liquid to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 6 to about 8or 9. The solid composition is configured to be contacted with a liquidto form a solution that comprises peroxyformic acid and has a pH rangingfrom about 4 to about 8 or 9, and the solution can maintain the pH rangefor any suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours. In a preferred aspect, the formed liquid, e.g., a solution,that comprises peroxyformic acid and has a pH near neutral, from about6-7 in a use solution.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid under any suitable conditions ortemperature. In some embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid at a temperatureranging from about −2° C. to about 60° C., 0° C. to about 60° C., or 4°C. to about 60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C.,4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C.,25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50°C., 50° C.-55° C., or 55° C.-60° C. In still other embodiments, thefirst reagent and the second reagent are configured to be contacted witheach other to form a liquid, e.g., a solution, that comprisesperoxyformic acid at a temperature at about 4° C. or lower than 4° C.,e.g., at about 3° C., 2° C., 1° C., 0° C., or lower than 0° C.

The solid composition can be configured to be contacted with a liquid toform a liquid, e.g., a solution, that comprises peroxyformic acid underany suitable conditions or temperature. In some embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises peroxyformic acid at a temperature ranging fromabout −2° C. to about 60° C., 0° C. to about 60° C., or 4° C. to about60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C., 4° C.-5° C.,5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25° C.-30°C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C., 50°C.-55° C., or 55° C.-60° C. In still other embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid at atemperature at about 4° C. or lower than 4° C., e.g., at about 3° C., 2°C., 1° C., 0° C., or lower than 0° C.

The present peroxyformic acid forming compositions can further comprisea catalyst (e.g. mineral acid) or an enzyme that catalyzes formation ofperoxyformic acid from the ester of a polyhydric alcohol and formicacid, and hydrogen peroxide. The present peroxyformic acid formingcompositions can comprise any suitable catalyst, e.g., a strong mineralacid, or enzyme, e.g., a perhydrolytic enzyme, lipase, coronase,termanyl or esperease. The catalyst or an enzyme can be comprised in anysuitable part of the present peroxyformic acid forming compositions. Insome embodiments, the first reagent comprises the catalyst or enzyme. Inother embodiments, the second reagent comprises the catalyst or enzyme.In still other embodiments, the present peroxyformic acid formingcompositions can further comprise a third reagent that comprises thecatalyst or enzyme. In yet other embodiments, the solid compositioncomprises the catalyst or enzyme.

The present peroxyformic acid forming compositions can further comprisea stabilizing agent for peroxyformic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent. In an aspect thestabilizing agent(s) and/or pH buffering agents are useful in decreasinga pH of the compositions to neutral or lower pH. The presentperoxyformic acid forming compositions can comprise any suitablestabilizing agent. Exemplary stabilizing agents include a phosphonatesalt(s) and/or a heterocyclic dicarboxylic acid, e.g., dipicolinic acid.In some embodiments, the stabilizing agent is pyridine carboxylic acidbased stabilizers, such as picolinic acid and salts,pyridine-2,6-dicarboxylic acid and salts, and phosphonate basedstabilizers, such as phosphoric acid and salts, pyrophosphoric acid andsalts and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)and salts. In other embodiments, the present peroxyformic acid formingcompositions comprise two or more stabilizing agents, e.g., HEDP and2,6-pyridinedicarboxylic acid (DPA). The stabilizing agent(s) can becomprised in any suitable part of the present peroxyformic acid formingcompositions. In some embodiments, the first reagent comprises astabilizing agent for peroxyformic acid and/or a pH buffering agent. Inother embodiments, the second reagent comprises a stabilizing agent forhydrogen peroxide. In still other embodiments, the present peroxyformicacid forming compositions can further comprise a third reagent thatcomprises a stabilizing agent for peroxyformic acid, a stabilizing agentfor hydrogen peroxide, and/or a pH buffering agent. In yet otherembodiments, the solid composition comprises a stabilizing agent forperoxyformic acid, a stabilizing agent for hydrogen peroxide, and/or apH buffering agent.

The present peroxyformic acid forming compositions can comprise anysuitable pH buffering agent. The pH buffer reagent can include anyreagent that is compatible with the ester(s) in the present peroxyformicacid forming compositions. Exemplary buffer agents suitable for usingwith a liquid ester can be an organic amine, such as triethanol amine,imidazole, etc. Exemplary buffer agents suitable for using with a solidform of ester include a broader range of buffers, such as a carbonatesalt, a phosphate salt, etc. The pH buffer reagent can be comprised inany suitable part of the present peroxyformic acid forming compositions.In some embodiments, the first reagent comprises a pH buffering agent.In other embodiments, the present peroxyformic acid forming compositionscan further comprise a third reagent that comprises a pH bufferingagent. In still other embodiments, the solid composition comprises a pHbuffering agent.

The present peroxyformic acid forming compositions can comprise anysuitable stabilizing agent for hydrogen peroxide. Exemplary stabilizingagents for hydrogen peroxide include phosphonates, heterocycliccarboxylic acids and the mixtures thereof. In some embodiments,stabilizing agents for hydrogen peroxide can be Dequest 2010, Dequest2066, Dipicolinic acids, etc. The stabilizing agent for hydrogenperoxide can be comprised in any suitable part of the presentperoxyformic acid forming compositions. In some embodiments, the secondreagent comprises a stabilizing agent for hydrogen peroxide. In otherembodiments, the present peroxyformic acid forming compositions canfurther comprise a third reagent that comprises a stabilizing agent forhydrogen peroxide. In still other embodiments, the solid compositioncomprises a stabilizing agent for hydrogen peroxide.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of an ester of a polyhydric alcohol and formicacid. For example, the first reagent of the peroxyformic acid formingcomposition can comprise any suitable concentration of an ester of apolyhydric alcohol and formic acid. In some embodiments, the formedliquid is a concentrate and comprises the first reagent in an amount upto about 90% of an ester of a polyhydric alcohol and formic acid. Inother embodiments, the formed liquid comprises the first reagent in anamount from about 1 ppm to about 500,000 ppm of an ester of a polyhydricalcohol and formic acid, or from about 10 ppm to about 500,000 ppm of anester of a polyhydric alcohol and formic acid. For example, the firstreagent in the formed liquid can comprise from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the first reagent in theformed liquid can comprise from about 50 ppm to about 40,000 ppm of anester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

In another example, the solid composition of the peroxyformic acidforming composition can comprise any suitable concentration of an esterof a polyhydric alcohol and formic acid. In some embodiments, the solidcomposition can provide a concentrate formed liquid that comprises thefirst reagent in an amount up to about 90% of an ester of a polyhydricalcohol and formic acid. In other embodiments, the solid composition canprovide for the formed liquid from about 10 ppm to about 500,000 ppm ofan ester of a polyhydric alcohol and formic acid. For example, the solidcomposition can provide for the formed liquid the ester of a polyhydricalcohol and formic acid in amounts comprising from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the solid composition canprovide for the formed liquid from about 50 ppm to about 40,000 ppm ofan ester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of hydrogen peroxide or a substance thatgenerates hydrogen peroxide upon contact with a liquid. For example, thesecond reagent of the peroxyformic acid forming composition can compriseany suitable concentration of hydrogen peroxide. In some embodiments, aconcentrate formed liquid comprises the second reagent in an amount upto about 10% of hydrogen peroxide. In some embodiments, the formedliquid comprises the second reagent in an amount comprising about 0.1ppm to about 100,000 ppm of hydrogen peroxide, or about 0.1 ppm to about100,000 ppm of hydrogen peroxide. For example, the second reagent in theformed liquid can comprise from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm,200,000-250,000 ppm, or 250,000-300,000 ppm hydrogen peroxide. In otherembodiments, the second reagent in the formed liquid comprises fromabout 150 ppm to about 50,000 ppm of hydrogen peroxide, e.g., about150-200, 150-300, 150-400, 150-500, 150-600, 150-700, 150-800, 150-900,150-1,000, 150-1,500, 150-2,000, 150-2,500, 150-3,000, 150-3,500,150-4,000, 150-4,500, 150-5,000, 150-10,000, 50-20,000, 50-30,000,50-40,000 or 50-50,000 ppm of hydrogen peroxide.

In some embodiments, a concentrate formed liquid comprises the secondreagent in an amount up to about 10% of hydrogen peroxide. In anotherexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1 ppm to about 100,000 ppm ofhydrogen peroxide upon contact with a liquid in the formed liquid. Forexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm hydrogen peroxide.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. For example, the first reagent andthe second reagent in the present peroxyformic acid forming compositionscan be configured to be contacted with each other to form a liquidand/or solid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. In some embodiments, the firstreagent and the second reagent can be configured to be contacted witheach other to form a liquid, e.g., a solution, that comprises from about0.1 ppm to about 100,000 ppm of peroxyformic acid, from about 0.1 ppm toabout 10,000 ppm of peroxyformic acid, or from about 0.1 ppm to about5,000 ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm or greater ofperoxyformic acid. In other embodiments, the first reagent and thesecond reagent can be configured to be contacted with each other to forma liquid, e.g., a solution, that comprises from about 1 ppm to about 500ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm,0.1-30 ppm, 0.1-40 ppm, 0.1-50 ppm, 0.1-60 ppm, 0.1-70 ppm, 0.1-80 ppm,0.1-90 ppm, 0.1-100 ppm, 0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0.1-300ppm, 0.1-350 ppm, 0.1-400 ppm, 0.1-450 ppm, 0.1-500 ppm of peroxyformicacid. In still other embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises from about 50 ppm to about 100ppm of peroxyformic acid, e.g., about 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm or 90-100 ppm of peroxyformic acid. In yet other embodiments,the first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises from about 200 ppm to about 300 ppm of peroxyformic acid,e.g., about 200-210 ppm, 210-220 ppm, 220-230 ppm, 230-240 ppm, 240-250ppm, 250-260 ppm, 260-270 ppm, 270-280 ppm, 280-290 ppm, 290-300 ppm ofperoxyformic acid.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid within any suitable time. Forexample, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid and/or solid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 1 ppmperoxyformic acid within 1 minute of the contact time, e.g., at leastabout 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm or greaterof peroxyformic acid within 1 minute of the contact time.

In an aspect, at least about 1 ppm peroxyformic is generated within lessthan 1 minute of contacting the first reagent and the second reagent. Inan aspect, at least about 1 ppm peroxyformic is generated within lessthan about 55 seconds, 50 seconds or less, 45 seconds or less, 40seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds orless, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5seconds or less. In an aspect, the reaction to form a liquid comprisingat least about 1 ppm peroxyformic acid is near instantaneous. In anaspect, at least about 100 ppm or at least about 500 ppm peroxyformic isgenerated within about 5 minutes or less of contacting the first reagentand the second reagent. In an aspect, at least about 100 ppm or 500 ppmperoxyformic is generated within less than about 4 minutes, 3 minutes orless, 2 minutes or less, or 1 minute or less.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitable percentageof the peak concentration of peroxyformic acid within any suitable time.For example, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid, e.g., a solution, that comprises anysuitable percentage of the peak concentration of peroxyformic acidwithin any suitable time. In some embodiments, the first reagent and thesecond reagent are configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 80% of the peakconcentration of peroxyformic acid within from about 5 minutes to about15 minutes of the contact time. For example, the first reagent and thesecond reagent are configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 80%, 85%, 90%,95%, 96%, 97%, 98%, 99% or 100% of the peak concentration ofperoxyformic acid within from about 5 minutes to about 15 minutes of thecontact time. In another example, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises at least about 80% of the peakconcentration of peroxyformic acid within from about 5, 6, 7, 8, 9, 10,11, 12, 13, 14 or 15 minutes of the contact time.

The formed peroxyformic acid can maintain any suitable percentage of thepeak concentration of peroxyformic acid within any suitable time. Insome embodiments, the formed peroxyformic acid can maintain at leastabout 50% of the peak concentration from about 5 minutes to about 25minutes after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.For example, the formed peroxyformic acid can maintain at least about50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or100% of the peak concentration from about 5 minutes to about 25 minutesafter the contact between the first reagent and the second reagent orafter the contact between the solid composition and a liquid. In anotherexample, the formed peroxyformic acid can maintain at least about 50% ofthe peak concentration from about 5-25 minutes, e.g., about 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25minutes, after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.In preferred aspects of the methods the desired peak concentration ofperoxyformic acid is 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, 5,000ppm, 6,000 ppm, 7,000 ppm, 8,000 ppm, 9,000 ppm, 10,000 ppm or more(inclusive of any ranges therein).

The present peroxyformic acid forming compositions can further comprisea C₂-C₂₂ percarboxylic acid, and wherein the first reagent or the solidcomposition comprising the first reagent and the second reagent are keptseparately from the C₂-C₂₂ percarboxylic acid prior to generateperoxyformic acid. The present peroxyformic acid forming compositionscan comprise any suitable C₂-C₂₂ percarboxylic acid, e.g., peroxyaceticacid, peroxyoctanoic acid and/or peroxysulfonated oleic acid. In anaspect, additional peroxycarboxylic acid compositions can be employed incombination with the peroxyformic acid composition. For example, C₁-C₂₄peroxycarboxylic acid, salt of C₁-C₂₄ peroxycarboxylic acid, ester ofC₁-C₂₄ peroxycarboxylic acid, or mixtures thereof. A carboxylic acid isan organic acid (R—COOH) which contains an aliphatic group and one ormore carboxyl groups. A carboxyl group is represented by —COOH, and isusually located at a terminal end of the acid. The aliphatic group canbe a substituted or unsubstituted group. Common aliphatic substituentsmay include —OH, —OR, —NO₂, halogen, and other substituents common onthese groups. An example of a simple carboxylic acid is acetic acid,which has the formula CH₃COOH. A peroxycarboxylic acid is a carboxylicacid which has been oxidized to contain a terminal —COOOH group. Theterm peroxy acid is often used to represent a peroxycarboxylic acid. Anexample of a simple peroxy acid is peroxyacetic acid, which has theformula CH₃COOOH.

Bleach Component

The bleach component for the methods include a source of active halogenor a halogen releasing substance suitable to liberate active halogenspecies such-as free elemental halogen (Cl, Br, Cl₂, Br₂) or —OCl— or—OBr—, under conditions normally used in detergent bleaching cleaningprocesses of a variety of cleaning targets. Preferably the halogenreleasing compound releases chlorine species. Chlorine releasingcompounds include potassium dichloroisocyanurate, sodiumdichloroisocyanurate, chlorinated trisodium phosphate, sodiumhypochlorite, calcium hypochlorite, lithium hypochlorite,monochloramine, dichloramine, [(monotrichloro)-tetra(monopotassiumdichloro)] pentaisocyanurate, 1,3-dichloro-5,5-dimethylidantonone,paratoluene sulfodichloro-amide, trichloromelamine, N-chloramine,N-chlorosuccinimide, N,N′-dichloroazodicarbonamide, N-chloroacetyl-urea,N,N-dichlorbiurile, chlorinated dicyandiamide, trichlorocyanuric acid,dichloroglycourea, etc. Chlorinated isocyanurate materials includingdichloroisocyanurate dihydrate, sodium dichloroisocyanurate, potassiumdichloroisocyanurate, etc. are preferred chlorine sources.

In another aspect, chlorine bleaches can be used in combination withN,N,N′,N′-tetraacetylethylenediamine (TAED)/perborate for bleachingproperties. In some aspects, a bleach activator and/or bleach catalystcan be employed.

Bleach Activators

The antimicrobial activity and/or bleaching activity of the methods isenhanced by the addition of a material which, when the composition isplaced in use, reacts or somehow interacts to form an activatedcomponent. For example, in some embodiments, a peracid or a peracid saltcan be formed. For example, in some embodiments, tetraacetylethylenediamine can be included within the composition to react with activeoxygen and form a peracid or a peracid salt that acts as anantimicrobial and bleaching agent. Other examples of active oxygenactivators include compounds that contain a carboxylic, nitrale, orester moiety, or other such compounds known in the art. Additionalexemplary activators include sodium nonanonyloxydenzene sulfonate(NOBS), acetyl caprolactone, and N-methyl morpholinium acetonitrile andsalts thereof (such as Sokalan BMG from BASF).

Bleach Catalysts

In some embodiments, the bleaching activity of the treatmentcompositions can be enhanced by the addition of a material which, whenthe composition is placed in use, reacts or somehow interacts to form anactivated component. For example, in some embodiments, transition metalcatalysts, especially those with iron or manganese, may be used.Surrounding the metals are ligands that typically contain nitrogen oroxygen. Effective ligand structures include1,4,7-trimethyl-1,4,7-triazacyclononane (Me₃-TACN),1,2,-bis-(4,7,-dimethyl-1,4,7,-triazacyclonon-1-yl)-ethane (Me₄-DTNE),N,N′,N″-tris[salicylideneaminoethyl]amine (saltren), tetraamidomacrocyclic ligand (TAML), bispyridyl pyrimidines and terpyridineligands. Especially preferred transition metal catalysts are manganesecontaining compounds sold commercially under the names Dragon andPegasus by Catexel. In some embodiments instead of adding a preformedcatalyst, the ligands may optionally be prepared without metal. Whenadded to the wash bath they may combine with trace metal ions naturallypresent in the wash water, or metal ions that have been intentionallyadded, to form a more active bleaching species in situ in the wash bath.Even in systems where there are no trace metal ions present in the waterthese ligands may bind to the metal ions present in stain for enhancedstain removal.

In a preferred aspect, the catalyst is a manganese containing compoundsold commercially under the names Dragon and Pegasus by Catexel.

It is also known that organic compounds can act catalytically to improvebleaching performance without combining with metal ions present ineither the wash water or the stain itself. Two general classes of suchmolecules are dioxiranes and oxaziridines. They are often formed in situby oxidation of ketones and imines, respectively. Dihydroisoquinolinederivatives are one especially preferred class of molecules formed inthis manner.

Adjuvants and Additional Functional Ingredients

The components for the methods of antimicrobial, disinfecting andbleaching laundry can further be combined with various functionalcomponents suitable for use in such applications, namely laundryapplications. In some embodiments, the steps of dosing a peroxyformicacid composition, an alkalinity source, a bleach activator and/orcatalyst in a detergent use solution, and optionally additional hydrogenperoxide make up a large amount, or even substantially all of the totalactives dosed into the washing application according to the methods. Forexample, in some embodiments few or no additional functional ingredientsare disposed therein.

In other embodiments, additional functional ingredients may be includedin the various dosing steps for the methods. The functional ingredientsprovide desired properties and functionalities to the peroxyformic acidcompositions, the alkalinity agents, and the detergent use solutions.For the purpose of this application, the term “functional ingredient”includes a material that when dispersed or dissolved in a use and/orconcentrate solution, such as an aqueous solution, provides a beneficialproperty in a particular use. Some particular examples of functionalmaterials are discussed in more detail below, although the particularmaterials discussed are given by way of example only, and that a broadvariety of other functional ingredients may be used. For example, manyof the functional materials discussed below relate to materials used ina laundry application. However, other embodiments may include functionalingredients for use in other applications.

In other embodiments, the compositions may include defoaming agents,anti-redeposition agents, bleaching agents, solubility modifiers,dispersants, rinse aids, metal protecting agents, stabilizing agents,corrosion inhibitors, additional sequestrants and/or chelating agents,fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes orcouplers, buffers, solvents and the like.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

Bleaching measurement of a laundry method was performed by using aTergotometer with 1 L pots and a water bath. First, the unwashedswatches from the lot numbers to be used in the test are read on aHunterLab Color Quest Spectrophotometer to establish the average initial(before washing) L value. This L value is a measurement for whiteness ona gray scale. A L value of 0 means black and a L value of 100 meanswhite. A sampling of 25 swatches of each type is typically used. Next,the desired wash temperature of 104° F. (40° C.) is programmed into theTergotometer and its water bath is allowed to heat up to thattemperature. One liter of the water type is added to each Tergotometerpot and allowed to equilibrate to the temperature.

The bleaching compositions tested are weighed out and added to theTergotometer pots.

Next, the swatches are added quickly to their respective pots in a leftto right sequence in order to minimize differences in exposure time tothe detergent systems. During this washing process, agitation is usuallyused throughout the process.

At the end of the run, the swatches are removed from the pots quickly ina left to right sequence using a forceps, then squeezed to remove excesswater, and finally left out to air dry.

Finally, the swatches are read on the HunterLab Color QuestSpectrophotometer and % soil removal is calculated as follows: % soilremoval=(Final L−Initial L)/(96−Initial L)*100.

In this example, peracid was initially added, followed by swatches andan alkaline source after 5 minutes, then followed by a manganesetransition metal catalyst after 6 minutes. The Tergetometer was run foran additional 4 minutes, leading to a total runtime of 10 minutes.Tested formulations are shown in Tables 1A and 1B. Target dosing isshown in Table 2 and results are shown in Table 3 with correspondingresults are depicted in FIG. 1. The final pH of the wash liquor was alsomeasured and is shown in Table 4.

TABLE 1A A PFA (Low H₂O₂) B PFA (Low H₂O₂) + Catalyst C PFA (Standard) DPFA (Standard) + Catalyst E PFA (Standard) + H₂O₂ (22 ppm) F PFA(Standard) + H₂O₂ (22 ppm) + Catalyst

TABLE 1B Active Formulation PFA (LOW H₂O₂) 6.7% PFA 0.74% H₂O₂ 74%Formic Acid 16.41% Water 2.1% methanesulfonic acid 0.05% dipicolinicacid PFA (Standard) 9.9% PFA 10% H2O2 32% Formic acid 46% Water 2.0%methanesulfonic acid

TABLE 2 Target PFA Dose Corresponding H₂O₂Dose Formula [ppm] [ppm] A 202 C 20 22

TABLE 3 Soil Removal Composition Swatch L* a* b* [%] A Coffee 76.61 2.4612.34 5.06 A Coffee 76.61 2.45 12.17 5.06 A Coffee 76.8 2.35 11.98 5.99A Tea 78.02 3.49 13.9 5.73 A Tea 78.51 3.36 13.41 8.30 A Tea 78.17 3.4113.46 6.52 A Coffee 76.15 2.43 12.22 2.81 A Coffee 76.39 2.34 11.79 3.99A Coffee 76.28 2.33 11.84 3.45 A Tea 77.27 3.58 13.88 1.80 A Tea 77.823.47 13.44 4.68 A Tea 77.76 3.42 13.18 4.37 B Coffee 76.83 2.61 12.66.14 B Coffee 76.78 2.51 12.22 5.90 B Coffee 76.89 2.48 12.13 6.43 B Tea77.95 3.57 13.95 5.36 B Tea 78.56 3.39 13.22 8.56 B Tea 78.85 3.32 13.4610.08 B Coffee 77.03 2.53 12.44 7.12 B Coffee 76.98 2.5 12.19 6.87 BCoffee 77.13 2.47 12.04 7.61 B Tea 77.86 3.58 14.11 4.89 B Tea 78.353.41 13.16 7.46 B Tea 78.44 3.42 13.31 7.93 C Coffee 77.25 2.47 12.668.20 C Coffee 76.79 2.49 12.51 5.94 C Coffee 77.16 2.4 12.19 7.76 C Tea78.63 3.44 14.58 8.93 C Tea 79.06 3.28 13.75 11.18 C Tea 78.85 3.3413.99 10.08 C Coffee 76.37 2.51 12.49 3.89 C Coffee 76.72 2.4 12.07 5.60C Coffee 76.69 2.42 12.14 5.45 C Tea 77.91 3.5 14.29 5.15 C Tea 78.323.43 14.01 7.30 C Tea 78.3 3.43 13.76 7.20 D Coffee 78.56 2.67 13.3814.61 D Coffee 78.96 2.55 12.81 16.57 D Coffee 79.15 2.5 12.69 17.50 DTea 81.19 3.02 14.26 22.35 D Tea 81.12 3.02 14.01 21.98 D Tea 81.4 2.9713.68 23.45 D Coffee 78.43 2.64 13.17 13.97 D Coffee 79.02 2.5 12.5616.86 D Coffee 79.12 2.52 12.73 17.35 D Tea 79.99 3.34 15.53 16.06 D Tea80.92 3.07 13.85 20.94 D Tea 81.07 3.01 13.73 21.72 E Coffee 77.05 2.5913.01 7.22 E Coffee 77.2 2.48 12.4 7.95 E Coffee 77.07 2.48 12.4 7.31 ETea 79.17 3.36 14.65 11.76 E Tea 79.23 3.31 14.19 12.07 E Tea 79.02 3.3114.23 10.97 E Coffee 76.89 2.56 12.75 6.43 E Coffee 77.09 2.46 12.247.41 E Coffee 77.17 2.42 12.17 7.80 E Tea 78.21 3.53 14.73 6.73 E Tea78.7 3.39 13.99 9.30 E Tea 78.64 3.37 14.02 8.98 F Coffee 79.99 2.5513.74 21.61 F Coffee 80.73 2.4 13.1 25.24 F Coffee 80.65 2.44 13.2524.84 F Tea 82.87 2.62 14.53 31.16 F Tea 83.27 2.51 13.66 33.26 F Tea82.94 2.59 13.9 31.53 F Coffee 80.36 2.54 13.54 23.42 F Coffee 80.832.43 13.05 25.72 F Coffee 80.43 2.43 12.98 23.77 F Tea 82.06 2.85 14.8626.91 F Tea 82.72 2.68 13.71 30.37 F Tea 82.32 2.74 13.8 28.28

TABLE 4 A 11.2 A 11.2 B 11.3 B 11.3 C 11.3 C 11.4 D 11.2 D 11.3 E 11.2 E11.3 F 11.2 F 11.3

As shown in the tables and FIG. 2, formulations containing low levels ofhydrogen peroxide containing PFA will not have a measurable bleachingeffect even if an oxygen catalyst is added to the system. The data showsthat a low peroxide PFA composition is not desired to neutralize thealkalinity in the wash methods and enhance bleaching efficacy. However,high hydrogen peroxide containing PFA formulations with the bleachingcomponent achieve an increase in bleaching efficacy through the additionof an oxygen catalyst.

Example 2

Titrations were completed using a dose of 20 ppm PFA of the formula C in1L of 5 grain water. Addition of 5% NaOH solution was completed prior tomeasurement of pH in order to obtain the titration curve shown in FIG.2. The titration was then repeated for an 80 ppm PAA. Both titrationswere completed at room temperature. Test conditions are summarized inTable 5. Raw data corresponding to FIG. 2 is shown in Table 6.

TABLE 5 Titration to given pH w 5% NaOH [mL] Peracid pH 7 pH 11 PFA (20ppm) 0.87* 3.60 PAA (80 ppm) 1.99* 5.03

TABLE 6 PFA (20 ppm) PAA (80 ppm) Dispensed [mL] pH Dispensed [mL] pH 05.88 0 4.98 0.005 5.88 0.025 4.98 0.01 5.88 0.05 5 0.015 5.89 0.1 5.020.02 5.9 0.15 5.07 0.025 5.91 0.2 5.1 0.03 5.92 0.25 5.14 0.035 5.93 0.35.17 0.04 5.93 0.35 5.21 0.045 5.94 0.4 5.25 0.05 5.95 0.45 5.29 0.0555.96 0.5 5.33 0.06 5.96 0.55 5.38 0.07 5.97 0.6 5.43 0.08 5.98 0.65 5.470.09 6 0.7 5.52 0.1 6.01 0.75 5.57 0.11 6.03 0.85 5.67 0.125 6.05 0.955.78 0.14 6.08 1 5.83 0.155 6.09 1.1 5.94 0.175 6.12 1.2 6.04 0.195 6.151.3 6.16 0.215 6.18 1.35 6.2 0.235 6.2 1.4 6.27 0.255 6.22 1.45 6.310.275 6.25 1.5 6.38 0.295 6.27 1.55 6.42 0.315 6.3 1.625 6.5 0.335 6.321.7 6.6 0.36 6.35 1.75 6.65 0.38 6.37 1.8 6.72 0.4 6.4 1.85 6.78 0.426.42 1.9 6.86 0.44 6.44 1.925 6.92 0.46 6.47 1.95 6.94 0.48 6.49 1.9756.98 0.5 6.51 2 7.02 0.52 6.54 2.1 7.22 0.54 6.56 2.175 7.36 0.58 6.62.25 7.55 0.6 6.63 2.325 7.72 0.62 6.65 2.4 7.89 0.64 6.68 2.5 8.12 0.666.71 2.6 8.32 0.68 6.73 2.75 8.66 0.7 6.75 2.875 8.94 0.72 6.78 3 9.210.74 6.8 3.125 9.42 0.76 6.83 3.25 9.6 0.78 6.86 3.375 9.76 0.8 6.89 3.59.89 0.82 6.92 3.625 10.02 0.84 6.95 3.75 10.13 0.86 6.98 3.85 10.220.88 7.02 3.925 10.29 0.9 7.05 4 10.35 0.92 7.09 4.125 10.45 0.94 7.114.25 10.55 0.96 7.13 4.375 10.64 0.98 7.18 4.5 10.72 1 7.21 4.55 10.751.025 7.23 4.6 10.78 1.075 7.35 4.65 10.82 1.125 7.49 4.7 10.84 1.1757.68 4.75 10.87 1.225 7.95 4.8 10.9 1.275 8.35 4.85 10.92 1.325 8.69 4.910.94 1.375 8.91 4.95 10.97 1.425 9.07 5 10.99 1.475 9.21 5.025 11 1.5259.32 5.05 11.01 1.575 9.41 1.625 9.49 1.675 9.57 1.725 9.63 1.775 9.71.85 9.78 1.925 9.86 2.025 9.96 2.15 10.07 2.25 10.15 2.35 10.24 2.42510.3 2.55 10.39 2.8 10.57 3 10.7 3.175 10.81 3.275 10.85 3.375 10.93.475 10.95 3.5 10.96 3.55 10.98 3.575 10.99 3.6 11 3.625 11 3.65 11.01

As shown in this Example the use of an acid in the first step requiresalkalinity to neutralize it. Beneficially since the peroxyformic acidcompositions are effective in the methods at lower doses, less acid isintroduced and therefore needs less alkalinity to neutralize.

Example 3

Microefficacy performance comparison between PAA and PFA formulations onKlebsiella pneumoniae (ATCC 4352) was compared at a dosing temperatureof 40° C. for 5 minutes of contact. Three sterile swatches (1″×1.5″)were inoculated with 0.03 mL of a prepared suspension containingKlebsiella pneumoniae. The carriers were then dried until visibly dryand aseptically placed between the sixth and seventh folds of a fabricwound spindle. The spindle was then placed into a chamber. Solutions ofPFA and PAA were then added to the chamber (75 g). The chamber wassecured into a laundrometer and run for 5 minutes at 40° C. After 5minutes, the carriers were neutralized separately and then diluted andplated to calculate log reductions. The wash water was also neutralizedand then diluted and plated to calculate log reductions.

PAA was dosed at a labeled rate for disinfection of textiles at (4oz/cwt; 60 gal/cwt for a 15.2% active solution). Table 7 shows theperformance of PAA at concentrations from 20 ppm to 80 ppm in comparisonto a PFA formulation with less than 20 ppm (17 ppm).

TABLE 7 Test Substance Coupon Log Reduction Concentration Klebsiella PAA80 ppm >4.02 PAA 60 ppm >3.90 PAA 40 ppm 3.15 PAA 20 ppm 2.07 PFA 17 ppm>5.12

As shown in Table 7 the PFA composition provided superior disinfectingproperties at a significantly lower actives when compared to PAA. Thisdata is significant as a lower ppm/active level of aantimicrobial/disinfecting peroxyformic acid composition can be dosedinto wash (such as laundry).

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

What is claimed is:
 1. A method of antimicrobial sanitizing and/ordisinfecting treatment and bleaching of laundry, the method comprising:a. washing the laundry with a peroxyformic acid composition at a pHrange from about 4 to about 7 in a laundry washing machine forantimicrobial efficacy on the laundry, wherein the peroxyformic acidcomposition comprises peroxyformic acid, formic acid and hydrogenperoxide; thereafter b. adding an alkalinity source to the washingmachine to increase the pH range to at least above 9 in the laundrywashing machine; thereafter c. adding a bleach activator and/or catalystcomposition to boost the bleaching efficacy of the peroxyformic acidcomposition on the laundry in the laundry washing machine; and d.optionally applying a detergent use solution to remove soil from thelaundry at any point in the method of sanitizing and/or disinfecting andbleaching of the laundry; e. draining the peroxyformic acid composition,the detergent use solution and the bleach activator and/or catalystcomposition from the laundry, wherein (i) the peroxyformic acidcomposition has a ratio of peroxyformic acid to hydrogen peroxide of 1:1or greater hydrogen peroxide, and/or (ii) the method comprises anadditional step of adding additional hydrogen peroxide to the wash ofthe laundry washing machine to increase the bleaching efficacy of theperoxyformic acid composition.
 2. The method of claim 1, wherein thelaundry washing machine is an industrial machine or a consumer machine.3. The method of claim 1, peroxyformic acid composition is applied tothe laundry in the laundry washing machine at a pH from about 5 to about8.
 4. The method of claim 1, wherein the peroxyformic acid compositionis applied to the laundry in the laundry washing machine for about 3 toabout 15 minutes.
 5. The method of claim 1, wherein the peroxyformicacid composition is generated in situ or at a point of use.
 6. Themethod of claim 1, wherein the peroxyformic acid composition is providedto the laundry washing machine at an actives level from about 5 ppm toabout 200 ppm.
 7. The method of claim 1, wherein the alkalinity sourceincreases the pH range to at least above
 10. 8. The method of claim 1,wherein the detergent use solution and the bleach activator and/orcatalyst composition is applied to the laundry in the laundry washingmachine for about 3 to about 15 minutes.
 9. The method of claim 1,wherein the detergent use solution comprises an alkalinity agent. 10.The method of claim 9, wherein the alkalinity agent comprises at leastone of alkali metal hydroxide, alkali metal silicate, alkali metalcarbonate or other base component.
 11. The method of claim 1, whereinthe detergent use solution further comprises any one or more ofsurfactants, chelants, polymers, enzymes, or other functionalingredients.
 12. The method of claim 1, wherein the bleach activator istetraacetylethylene diamine, sodium nonanonyloxydenzene sulfonate(NOBS), acetyl caprolactone, N-methyl morpholinium acetonitrile orcombinations thereof.
 13. The method of claim 1, wherein the bleachcatalyst is a transition metal catalyst.
 14. The method of claim 13,wherein the transition metal catalyst is a manganese containingcompound.
 15. The method of claim 1, further comprising a step of addingadditional hydrogen peroxide to the wash of the laundry washing machinebefore or after the addition of the peroxyformic acid composition,before or after the addition of the detergent use solution, before orafter the addition of the alkalinity source, and/or before or after theaddition of the bleach activator and/or catalyst to increase thebleaching efficacy of the peroxyformic acid composition.
 16. The methodof claim 1, further comprising a step of rinsing the peroxyformic acidcomposition, the detergent use solution and the bleach activator and/orcatalyst composition from the laundry.
 17. The method of claim 16,wherein the laundry is rinsed with water in the laundry washing machinefor at least about 1 minute.
 18. The method of claim 1, wherein themethod further comprises an adjuvant use solution comprising at leastone of souring agents, fabric softening agents, starch, anti-wrinkleagents, sizing agents, color-fastness agents, oil and water repellantagents, water conditioning agents, iron controlling agents, waterthreshold agents, soil releasing agents, soil shielding agents, opticalbrightening agents, fragrances, and mixtures thereof, and wherein theadjuvant use solution is applied to the laundry in the laundry washingmachine at a pH from about 5 to about 8 for about 1 to about 6 minutes.19. The method of claim 1, wherein the method of sanitizing and/ordisinfecting and bleaching laundry follows an initial washing step forthe laundry.